CN104120467B - Copper-zinc-tin film material with controllable components, copper-zinc-tin sulfenyl solar battery and preparation method of the two - Google Patents
Copper-zinc-tin film material with controllable components, copper-zinc-tin sulfenyl solar battery and preparation method of the two Download PDFInfo
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Abstract
The invention discloses a preparation method of a copper-zinc-tin film material. The preparation method comprises the following steps: (1) the copper-zinc-tin film material comprises at least three main metal elements of copper, zinc and tin; electroplate liquid contains any two main metal elements; and additive solution contains a third main metal element; (2) at least one conducting electrode serves as a first electrode in the electroplate liquid; and a film substrate to be plated serves as a second electrode; (3) when electricity is conducted between the first electrode and the second electrode, and the speed is controlled to add the additive solution, that is, films containing three metals of copper, zinc and tin are synchronously deposited to obtain a substrate deposited with the copper-zinc-tin metal film on the surface; and the copper-zinc-tin film material is obtained. In the preparation method of a copper-zinc-tin sulfenyl solar battery, a cadmium sulfide buffer layer, a ZnO film and an ITO film or an AZO film are deposited on the copper-zinc-tin film material in sequence to obtain the copper-zinc-tin sulfenyl solar battery after the step (4).
Description
Technical field
The present invention relates to the thin film solar cell in photoelectric material and technical field of new energies, specially a kind of composition is controlled
Copper zinc-tin thin-film material and copper-zinc-tin-sulfur based solar battery and both preparation method.
Background technology
With the minimizing of the non-renewable energy resources reserves such as fossil fuel, sustainable clean reproducible energy, such as solar energy, wind
Can, biological energy source, tide energy etc. is of great interest.Especially solar energy, inexhaustible as one kind, right
The new forms of energy of environmental nonpollution, become with fastest developing speed, the field attracting most attention, and are solve world energy sources crisis now effective
Means.Photovoltaic generation is the important means using solar energy, and therefore the research to solar cell gets more and more now.
Current solar cell is mainly based on monocrystalline silicon and polysilicon, but production cost is too high, and light decay effect is obvious.
Thin film solar cell is with the advantage of silicon solar cell high conversion efficiency and inexpensive, simultaneously high to the absorption coefficient of light, is
A kind of more promising solar cell material.Copper indium gallium selenide film battery is that current technology is the most ripe, and efficiency highest is thin
Film solar cell, but indium and gallium are rare and scatter elements, expensive and reserves are limited.At present most study, be considered to have most
The alternative materials of potentiality are to substitute the copper-zinc-tin-sulfur film material of in and ga with zn and sn, the sun electricity of its laboratory preparation at present
Pond highest conversion efficiency has reached 12.6%.
The preparation of copper-zinc-tin-sulfur film mainly has vacuum method and two kinds of antivacuum method.Vacuum method has magnetron sputtering method, and heat is steamed
Send out, pulsed laser deposition etc., antivacuum method has electrochemical deposition, sol-gel, spray pyrolysis etc..Comparatively speaking vacuum method
The sample quality of preparation is high, but the high condition of process costs is harsh, and antivacuum method low cost, it is less demanding to process conditions,
Thus obtained bigger attention.Wherein electrochemical deposition method has lot of advantages: as controlled in electrochemical process parameter, repeatability
High；Less demanding to experimental facilities, low cost, room temperature can be carried out；Simple and fast, and thin film deposition is more uniform.
Electrochemically depositing copper-zinc-tin sulphur mainly has two methods at present, i.e. the method for fractional steps and co-electrodeposition method.The method of fractional steps be by copper,
Zinc, three metals of tin are sequentially deposited in substrate, are then vulcanized.The advantage of the method is that three metallic solutions are stable, can
To be recycled for multiple times, simple to operate.However it is necessary that strictly controlling every layer of quality and thickness to adjust the stoichiometry of film layer
Than, and need to control every layer of pattern, because coarse substrate can make next layer of metal surface more coarse, it is also contemplated that electrochemical
Learn the edge effect of deposition, that is, working electrode substrate top edge and center deposition variable thickness cause.Second method is codeposition
Method, will three metals of copper zinc-tin be concurrently deposited in substrate, then carries out sulfuration synthesis copper-zinc-tin-sulfur film again.The method needs
Strictly to control the relative concentration of three metallic solutions of copper zinc-tin, the ph of solution, temperature and deposition voltage.Due to copper zinc-tin three
The reduction potential gap of metal is larger, therefore hardly results in the copper-zinc-tin-sulfur film of proper ratio, and three kinds of slaines are blended in
Together, stability of solution is not high.Two methods are compared, the film of method of fractional steps preparation, Composition Control is good but crystallinity not
Good, and co-deposit the bad control of composition but good crystallinity；Therefore all cannot meet preparation and the use requirement of copper-zinc-tin-sulfur film.
Content of the invention
For in prior art propose problem, the present invention provide one kind can not only precise control deposition fraction, and
Excellent in crystallinity, form the preparation side of controlled copper zinc-tin thin-film material and copper-zinc-tin-sulfur based solar battery and both
Method.
The present invention is to be achieved through the following technical solutions:
A kind of preparation method of present invention copper zinc-tin thin-film material, comprises the steps:
1) copper zinc-tin thin-film material contains at least copper, zinc and three kinds of base metal elements of tin；Three kinds of masters are contained in electroplate liquid
In body metallic element any two kinds；Annex solution contains the third base metal element lacking in described electroplate liquid；
2) there is at least one conductive electrode in electroplate liquid as first electrode, film-substrate to be plated is as second electrode；
Described film-substrate to be plated is the substrate that conductive substrates or surface are coated with conductive film；
3), when being energized between first electrode and second electrode, speed control adds annex solution, that is, start to deposit simultaneously cupric,
Zinc and the film of three kinds of metals of tin, obtain the substrate of copper-depositing on surface zinc-tin metallic film, as copper zinc-tin thin-film material；In electricity
During plating, second electrode current potential opposite first pole is negative.
Preferably, in step 3) after, by the silicon of copper-depositing on surface zinc-tin metallic film to 200～400 DEG C of temperature
The lower process of degree obtains Jackson's alloy thin-film material in 20～60 minutes.
Preferably, in step 3) after, copper zinc-tin thin-film material or Jackson's alloy thin-film material are exposed to sour gas
Atmosphere, processes 1～40 minute at a temperature of being heated to 400～700 DEG C, prepares copper-zinc-tin-sulfur film material.
Preferably, in step 3) after, by copper zinc-tin thin-film material or Jackson's alloy thin-film material be exposed to sulfur-bearing and
Selenium atmosphere, processes 1～40 minute at a temperature of being heated to 400～700 DEG C, prepares copper zinc tin sulfur selenium thin-film material；Film material
The ratio of sulphur and selenium in material, is adjusted by the ratio controlling sulphur and selenium in atmosphere.
Preferably, step 1) in electroplate liquid be dissolved in water and made by the slaine of zinc-tin or copper and tin or zinc-tin and complex compound,
Respective salt concentration range is 0.01～1m, and complex compound is hydroxide, thiosulfate, sulphite, citrate, burnt phosphorus
One or more of hydrochlorate, tartaric acid, tartrate and cyanide, complex concentration scope is 0.01～0.5m.
Further, step 1) in annex solution water be dissolved in by the third plating metal salt and complex compound make, salinity model
Enclose for 0.01～1m, complex compound is hydroxide, thiosulfate, sulphite, citrate, pyrophosphate, tartaric acid, wine
One or more of stone hydrochlorate and cyanide, complex concentration scope is 0.1～0.5m.
Preferably, step 2) in, the plated film part of the addition total amount submergence film-substrate to be plated of electroplate liquid and annex solution；Treat
Plating film-substrate is connected with negative electrode, and first electrode is connected with anode, has been independently arranged reference electrode in electroplate liquid；Adjust before plating
Electroplate liquid ph value is to 2～6；Applied voltage -10～0v between the first electrode and the second electrode during plating, distance for 0.2～
20cm, during plating, electroplate liquid keeps 20-80 DEG C of constant temperature.
Preferably, the surface of employing is coated with the substrate of conductive film, and conductive film is gold that thickness is 0.1～10 micron
Belong to or metal-oxide film.
Further, film-substrate to be plated is rigid substrate, and rigid substrate includes metal substrate, silicon chip and is coated with conductive film
Glass substrate or ceramic substrate.
Further, metal substrate includes copper sheet, aluminium flake and stainless steel substrates；Described glass substrate includes being coated with fto's
Glass and the glass being coated with ito.
Further, film-substrate to be plated is the flexible substrate including metal forming and polymer membrane.
Further, flexible substrate passes through electroplate liquid in reel-to-reel mode, prepares copper zinc-tin metal foil on flexible substrates
Film.
A kind of controlled copper zinc-tin thin-film material of composition of the present invention, by any one copper zinc-tin thin-film material above-described
Preparation method be obtained.
Preferably, the thickness of copper zinc-tin thin-film material is 500～5000 nanometers.
Further, the thickness of copper zinc-tin thin-film material be 1000～3000 nanometers, copper zinc-tin thickness of metal film be 700～
1500 nanometers.
A kind of preparation method of present invention copper-zinc-tin-sulfur based solar battery, in a kind of any of the above copper zinc-tin thin-film material
Preparation method step 3) after, also comprise the steps: to be sequentially depositing cadmium sulfide cushion on copper zinc-tin thin-film material
Obtain copper-zinc-tin-sulfur based solar battery with after zno film and ito film or azo film.
A kind of present invention copper-zinc-tin-sulfur based solar battery, by the preparation method of copper-zinc-tin-sulfur based solar battery of the present invention
It is obtained.
Compared with prior art, the present invention has a following beneficial technique effect:
The preparation method of copper zinc-tin thin-film material of the present invention, by configuring the plating solution of ion-conductance containing binary metal, then
Deposition during control drop rate add containing the third metallic element annex solution it is ensured that three kinds of metallic elements same
When deposition.By the nonuniform deposition that the electrical potential difference between three kinds of metallic elements is brought is reduced to the control adding speed, will
Ternary codeposition is changed to the controlled binary codeposition of the third metallic solution addition, makes the control of electro-deposition increased a dimension
Degree.Simple and convenient, stable performance, prepare the controlled copper zinc-tin thin-film material of metal ratio it is adaptable to follow-up solar-electricity
The preparation of pond device and industrial applications.Because by three kinds of metallic elements, mixed deposit, on substrate, is electroplated with lamination simultaneously
The technique of three kinds of metallic elements is compared, and the present invention, without the long range diffusion of element, reduces the time required for subsequent treatment.
Further, by processing the alloyed activator of film-substrate to be plated so as to surface state can be good at reality
The initial stage nucleation of existing film and enhancing adhesion, preferably improve the quality of thin-film material.
Further, by being heated in the atmosphere of sulfur-bearing or sulfur-bearing and selenium, corresponding copper zinc can be obtained
Tin thin film material, adapts to different use demands, on the basis of alloying heats, can be complete in the short time at high temperature
One-tenth is processed, and preferably improves the photoelectric properties of thin-film material, product stability and high efficiency, and can pass through to control sulphur or selenium in atmosphere
Ratio, reach the purpose of regulation, realize controllable operating.
Further, the present invention passes through slaine and complex compound is dissolved jointly, and using sulfate or other appearances
Easily decompose the salt of volatilization, thus avoiding other impurities ion pair film morphology and battery effect in the quaternary sulfide finally producing
The impact of rate is it is ensured that the quality of the film of preparation is it is easy to large-area industrially prepared, with low cost.
Further, the present invention is defined to each influence factor in electrodeposition process, by preferably electrochemistry
The temperature of deposition, ph, the restriction of electrolyte concentration, complex ion concentration and deposition voltage are finally obtained optimal deposition metal foil
The experiment condition of film.Bath temperature can affect the current efficiency when negative electrode deposits for the metal；The one-tenth to alloy layer for the sedimentation potential
Film quality has a significant impact；Stirring, additive, concentration of metal ions and complexing agent concentration can directly influence the group of alloy layer
Point.In addition this programme carries out electrochemical deposition using three-electrode system, and system is more stable, and the result of acquisition is more credible.
Further, using rigid substrate such as silicon chip or glass, to the pattern of metal back electrode and copper-zinc-tin-sulfur film,
Nucleation, growth and preferred orientation generation Beneficial Effect, and ensure that the reprocessing of subsequent product, especially in soda-lime glass substrate
Sodium element is diffused with to upper strata and is beneficial to grow high-quality copper zinc-tin-sulfur film.
Further, copper-zinc-tin-sulfur film is prepared by flexible substrate, the solar cell enabling to reaches high
Mass-power ratio, and it is low to produce preparation cost, is suitable for architecture-integral, is particularly suitable for the solar energy on uneven roof
Battery uses.The flexible battery made can cut into any shape and size, can also make photovoltaic tiles simultaneously；It is suitable for big rule
The volume to volume technique productions of mould, and there is foldability and non-friable characteristic, practical application is strong.
Further, volume to volume mode deposition prepares copper zinc selenium metallic film, contributes to copper zinc-tin based thin film solar electricity
Pond industrializes, by preferably ph, deposition voltage, stir speed (S.S.), the rate of addition of the third solution control it is ensured that optimal
The preparation condition of deposition copper zinc selenium metallic film, is easy to industrialized production.
The controlled copper zinc-tin thin-film material of present invention composition, by the restriction of copper zinc selenium thickness of metal film, for subsequently electricity
Pond device preparation provides good basis, is conducive to improving battery efficiency.
Copper-zinc-tin-sulfur film solar cell of the present invention and preparation method thereof, on the basis of the thin-film material of preparation
On, by the deposition of cushion and conducting window layer and control, completing the preparation of solar cell and its lifting of performance,
The method processing is simple, and membrane quality is excellent.
Brief description
Fig. 1 is the preparation technology flow chart of the copper-zinc-tin-sulfur film material described in present example.
Fig. 2 is the sem figure that copper-zinc-tin-sulfur film material is obtained in present example.
Fig. 3 is the xrd figure that copper-zinc-tin-sulfur film material is obtained in present example.
Fig. 4 is the raman figure that copper-zinc-tin-sulfur film material is obtained in present example.
Fig. 5 is the copper-zinc-tin-sulfur film battery cross sectional sem figure doing in molybdenum glass substrate in present example.
Fig. 6 is the i-v figure that copper-zinc-tin-sulfur film solar cell is obtained in present example.
Fig. 7 be in present example copper zinc-tin thin-film material with the preparation facilities schematic diagram of reel-to-reel mode.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, described be explanation of the invention and
It is not to limit.
A kind of preparation method of present invention copper zinc-tin thin-film material, it comprises the steps:
1) copper zinc-tin thin-film material contains at least copper, zinc and three kinds of base metal elements of tin；Three kinds of masters are contained in electroplate liquid
In body metallic element any two kinds；Annex solution contains the third base metal element lacking in described electroplate liquid；
2) there is at least one conductive electrode in electroplate liquid as first electrode, film-substrate to be plated is as second electrode；
Described film-substrate to be plated is the substrate that conductive substrates or surface are coated with conductive film；
3), when being energized between first electrode and second electrode, speed control adds annex solution, that is, start to deposit simultaneously cupric,
Zinc and the film of three kinds of metals of tin, obtain the substrate of copper-depositing on surface zinc-tin metallic film, as copper zinc-tin thin-film material；In electricity
During plating, second electrode current potential opposite first pole is negative.
In step 3) after, the silicon of copper-depositing on surface zinc-tin metallic film can be located at a temperature of 200～400 DEG C
Reason obtains Jackson's alloy thin-film material in 20～60 minutes；Can also be by copper zinc-tin thin-film material or Jackson's alloy thin-film material
It is exposed to sulfur-bearing atmosphere, 1～40 minute at a temperature of being heated to 400～700 DEG C, prepare copper-zinc-tin-sulfur film material.Also copper
Zinc-tin thin-film material or Jackson's alloy thin-film material can be exposed to sulfur-bearing and selenium atmosphere, is heated to 400～700 DEG C of temperature
Lower 1～40 minute, prepare copper zinc tin sulfur selenium thin-film material；The ratio of sulphur and selenium in thin-film material, by control sulphur and selenium gas
Proportion adjustment in atmosphere.Preparation technology flow chart as shown in Figure 1, the copper-zinc-tin-sulfur film material obtaining by as above method each
Item performance is as shown in Fig. 2-Fig. 6.
Fig. 2 schemes for sem, and the copper-zinc-tin-sulfur film surfacing after as can be seen from the figure annealing is fine and close, and particle uniformly divides
Almost without cavity between cloth, and particle, suitable further battery preparation.
Fig. 3 schemes for xrd: for the czts film using electrochemical deposition, sulfuration annealing plays vital effect.
Can be seen that all films from xrd diffraction maximum and all assume stronger (112) of czts, (211), (200), (220) and (312) are special
Levy peak, in addition it was found that (110) and (211) diffraction maximum of mo substrate, the no diffraction maximum of other Binary-phase impurity.By
In cu2znsns4, zns and cu2sns3Diffraction maximum very nearly the same, therefore tested using raman further.
Fig. 4 schemes for raman: in 251cm-1、287cm-1、338cm-1And 368cm-1The vibration peak at place is all corresponding to be czts
Thing phase, this analysis result with xrd coincide.It is not detected by zns and cu2sns3Thing phase, the preparation of this method is described
Czts thing is compared pure.
Fig. 5 is the sem sectional view of copper-zinc-tin-sulfur film battery: the copper-zinc-tin-sulfur being obtained by preparation method of the present invention is thin
The section of film solar cell as illustrated, as seen from the figure back electrode molybdenum layer thickness be about 1 μm, have 100nm between mo and czts
The molybdenum sulfide of left and right generates, and the czts absorber thickness of particle even compact is about 800nm, be followed successively by above cushion cds and
I-zno and azo.
Fig. 6 is device efficiency analysis chart, the knot of the czts thin-film solar cells being obtained by preparation method of the present invention
Structure is mo/czts/cds/i-zno/azo, in room temperature am1.5 and 1000w/m2Under the conditions of the i-v characteristic curve that records as schemed
Show.The czts hull cell of reported first the method preparation, battery efficiency is 1.60%.
Specific preparation process such as example 1 below -35.
Example 1
A kind of preparation method of present invention copper zinc-tin thin-film material, step is as follows:
Configuration zinc-tin binary metal mixed solution does electrolyte: 0.07m zinc sulfate, the STANNOUS SULPHATE CRYSTALLINE of 0.05m, sodium citrate network
Mixture, ph is 3.Configure the third metal salt solution and do annex solution: 0.4m copper sulphate, sodium citrate is complexing agent.Substrate is made
It is connected with the conductive electrode as first electrode for second electrode and be placed in electrolyte, the current potential opposite first pole of second electrode
It is negative.Speed control adds annex solution, and addition is 15ml/min, starts to deposit copper, zinc, tin using the fixed potential same time
Three kinds of metals, form metallic film, and current potential is -1.7v, sedimentation time 10min, obtain copper-depositing on surface zinc-tin after completing plating
The substrate of metallic film, i.e. copper zinc-tin thin-film material.
Example 2
A kind of preparation method of present invention copper zinc-tin thin-film material, step is as follows:
Configuration copper zinc binary metal mixed solution: 0.08m zinc sulfate, the copper sulphate of 0.01m, sodium citrate complexing agent, ph
For 6.Configure the third metal salt solution and do annex solution: 0.3m STANNOUS SULPHATE CRYSTALLINE, sodium citrate is complexing agent.Using substrate as the second electricity
Pole is connected with the conductive electrode as first electrode and is placed in electrolyte, and the current potential opposite first pole of second electrode is negative.Control
Speed processed adds annex solution, and addition is 10ml/min, starts to deposit copper, zinc, three kinds of gold of tin using the fixed potential same time
Belong to, form metallic film, current potential is -1.7v, sedimentation time 7min, after completing plating, obtain copper-depositing on surface zinc-tin metallic film
Substrate, i.e. copper zinc-tin thin-film material.
Example 3
A kind of preparation method of present invention copper zinc-tin thin-film material, step is as follows:
Configuration copper and tin binary metal mixed solution: 0.02m copper sulphate, the STANNOUS SULPHATE CRYSTALLINE of 0.01m, sodium citrate complexing agent, ph
For 5.Configure the third metal salt solution and do annex solution: 0.3m zinc sulfate, sodium citrate is complexing agent.Using substrate as the second electricity
Pole is connected with the conductive electrode as first electrode and is placed in electrolyte, and the current potential opposite first pole of second electrode is negative.Control
Speed processed adds annex solution, and addition is 15ml/min, starts to deposit copper, zinc, three kinds of gold of tin using the fixed potential same time
Belong to, form metallic film, current potential is -1.75v, sedimentation time 15min, after completing plating, obtain copper-depositing on surface zinc-tin metal foil
The substrate of film, i.e. copper zinc-tin thin-film material.
Example 4
A kind of preparation method of present invention copper zinc-tin thin-film material, step is as follows:
Configuration zinc-tin binary metal mixed solution does electrolyte: 0.08m zinc sulfate, the STANNOUS SULPHATE CRYSTALLINE of 0.01m, sodium citrate network
Mixture, ph is 4.Configure the third metal salt solution and do annex solution: 0.3m copper sulphate, sodium citrate is complexing agent.Substrate is made
It is connected with the conductive electrode as first electrode for second electrode and be placed in electrolyte, the current potential opposite first pole of second electrode
It is negative.Speed control adds annex solution, and addition is 8ml/min, starts to deposit copper, zinc, tin using the fixed potential same time
Three kinds of metals, form metallic film, and current potential is -1.75v, sedimentation time 8min, obtain copper-depositing on surface zinc-tin after completing plating
The substrate of metallic film, i.e. copper zinc-tin thin-film material.
Example 5
A kind of preparation method of present invention copper zinc-tin thin-film material, step is as follows:
Configuration copper zinc binary metal mixed solution: 0.01m zinc sulfate, the copper sulphate of 0.05m, sodium citrate complexing agent, ph
For 3.Configure the third metal salt solution and do annex solution: 0.5m STANNOUS SULPHATE CRYSTALLINE, sodium citrate is complexing agent.Using substrate as the second electricity
Pole is connected with the conductive electrode as first electrode and is placed in electrolyte, and the current potential opposite first pole of second electrode is negative.Control
Speed processed adds annex solution, and addition is 3ml/min, starts to deposit copper, zinc, three kinds of gold of tin using the fixed potential same time
Belong to, form metallic film, current potential is 0v, sedimentation time 14min, after completing plating, obtain copper-depositing on surface zinc-tin metallic film
Substrate, i.e. copper zinc-tin thin-film material.
Example 6
A kind of preparation method of present invention copper zinc-tin thin-film material, step is as follows:
Configuration zinc-tin binary metal mixed solution does electrolyte: 0.8m zinc sulfate, the STANNOUS SULPHATE CRYSTALLINE of 0.6m, and sodium citrate is complexed
Agent, ph is 5.Configure the third metal salt solution and do annex solution: 1m copper sulphate, sodium citrate is complexing agent.Using substrate as
Two electrodes are connected with the conductive electrode as first electrode and are placed in electrolyte, and the current potential opposite first pole of second electrode is
Negative.Speed control adds annex solution, and addition is 0.26ml/min, starts to deposit copper, zinc, tin using the fixed potential same time
Three kinds of metals, form metallic film, and current potential is -2v, sedimentation time 12min, obtain copper-depositing on surface zinc-tin gold after completing plating
Belong to the substrate of film, i.e. copper zinc-tin thin-film material.
Example 7
A kind of preparation method of present invention copper zinc-tin thin-film material, step is as follows:
Configuration copper and tin binary metal mixed solution: 0.4m copper sulphate, the STANNOUS SULPHATE CRYSTALLINE of 0.7m, sodium citrate complexing agent, ph is
2.Configure the third metal salt solution and do annex solution: 1m zinc sulfate, sodium citrate is complexing agent.Using substrate as second electrode with
As first electrode conductive electrode be connected be placed in electrolyte, the current potential opposite first pole of second electrode is negative.Control speed
Rate adds annex solution, and addition is 0.14ml/min, starts to deposit copper, zinc, three kinds of metals of tin using the fixed potential same time,
Form metallic film, current potential is -4v, sedimentation time 9min, after completing to electroplate, obtain the lining of copper-depositing on surface zinc-tin metallic film
Bottom, i.e. copper zinc-tin thin-film material.
Example 8
A kind of preparation method of present invention copper zinc-tin thin-film material, step is as follows:
Configuration copper zinc binary metal mixed solution: 0.06m zinc sulfate, the copper sulphate of 0.13m, sodium citrate complexing agent, ph
For 4.Configure the third metal salt solution and do annex solution: 1m STANNOUS SULPHATE CRYSTALLINE, sodium citrate is complexing agent.Using substrate as second electrode
It is connected with the conductive electrode as first electrode and is placed in electrolyte, the current potential opposite first pole of second electrode is negative.Control
Speed adds annex solution, and addition is 0.10ml/min, starts to deposit copper, zinc, three kinds of gold of tin using the fixed potential same time
Belong to, form metallic film, current potential is -3v, sedimentation time 11min, after completing plating, obtain copper-depositing on surface zinc-tin metallic film
Substrate, i.e. copper zinc-tin thin-film material.
Example 9
A kind of preparation method of present invention copper zinc-tin thin-film material, step is as follows:
Configuration copper zinc binary metal mixed solution: 0.41m zinc sulfate, the copper sulphate of 0.75m, sodium citrate complexing agent, ph
For 4.Configure the third metal salt solution and do annex solution: 0.01m STANNOUS SULPHATE CRYSTALLINE, sodium citrate is complexing agent.Using substrate as second
Electrode is connected with the conductive electrode as first electrode and is placed in electrolyte, and the current potential opposite first pole of second electrode is negative.
Speed control adds annex solution, and addition is 13ml/min, starts to deposit copper, zinc, three kinds of tin using the fixed potential same time
Metal, forms metallic film, and current potential is -10v, sedimentation time 6min, obtains copper-depositing on surface zinc-tin metal foil after completing plating
The substrate of film, i.e. copper zinc-tin thin-film material.
Example 10
A kind of preparation method of present invention copper zinc-tin thin-film material, step is as follows:
Configuration zinc-tin binary metal mixed solution does electrolyte: 0.37m zinc sulfate, the STANNOUS SULPHATE CRYSTALLINE of 0.26m, sodium citrate network
Mixture, ph is 6.Configure the third metal salt solution and do annex solution: 0.01m copper sulphate, sodium citrate is complexing agent.Substrate is made
It is connected with the conductive electrode as first electrode for second electrode and be placed in electrolyte, the current potential opposite first pole of second electrode
It is negative.Speed control adds annex solution, and addition is 14ml/min, starts to deposit copper, zinc, tin using the fixed potential same time
Three kinds of metals, form metallic film, and current potential is -7v, sedimentation time 13min, obtain copper-depositing on surface zinc-tin gold after completing plating
Belong to the substrate of film, i.e. copper zinc-tin thin-film material.
Example 11
A kind of preparation method of present invention copper zinc-tin thin-film material, step is as follows:
Configuration copper and tin binary metal mixed solution: 0.50m copper sulphate, the STANNOUS SULPHATE CRYSTALLINE of 0.65m, sodium citrate complexing agent, ph
For 3.Configure the third metal salt solution and do annex solution: 0.01m zinc sulfate, sodium citrate is complexing agent.Using substrate as second
Electrode is connected with the conductive electrode as first electrode and is placed in electrolyte, and the current potential opposite first pole of second electrode is negative.
Speed control adds annex solution, and addition is 1.2ml/min, starts to deposit copper, zinc, three kinds of tin using the fixed potential same time
Metal, forms metallic film, and current potential is -9v, sedimentation time 5min, obtains copper-depositing on surface zinc-tin metallic film after completing plating
Substrate, i.e. copper zinc-tin thin-film material.
Example 12
In example 1-11, any one sulfate ion in zinc sulfate, STANNOUS SULPHATE CRYSTALLINE and copper sulphate can be by other
Acid ion replaces forming corresponding slaine, carries out remaining operation, wherein preferably acid ion be nitrate ion and
Chlorion, and when with once electroplating, zinc, tin and copper can be carried out in conjunction with different acid ions.
Embodiment 13
In example 1-12, the complex compound in electroplate liquid and annex solution all can adopt hydroxide, thiosulfate, Asia
One of sulfate, the citrate including sodium citrate, pyrophosphate, tartaric acid, tartrate and cyanide or
Several, in electroplate liquid, the concentration of complex compound is preferably 0.01～5m, and the concentration of complex compound preferably 0.1 in annex solution～
5m, specific complex compound type and concentration all can be selected according to the dissolubility of corresponding slaine.
Example 14
In example 1-13, speed control add annex solution when, annex solution add when can using peristaltic pump, liquid-transfering gun,
Buret or graduated cylinder enter between-line spacing or lasting or carrying out dropwise and add it is ensured that wherein the third base metal element
Adding rate and sedimentation rate reach dynamic equilibrium, that is, the speed added and the speed depositing reach equal, and the amount of addition can
Meet demand during its deposition, but make addition speed destroy stability of solution or three kinds of base metal units not over its demand
The crystallinity of element.Wherein, by controlling drop rate so that the deposition of ion that gets on of additions speed and the electro-deposition of annex solution
Speed reaches dynamic equilibrium, makes depositional control accurately, deposition film uniform smooth.
Example 15
In example 1-11, as long as first electrode conductive electrode to finally obtain copper zinc-tin thin-film material not
The electrode that impact can be produced all can adopt, and is connected with anode, wherein preferably adopts platinum electrode or graphite in inert electrode
Electrode；Second electrode is connected with negative electrode, and the distance between first electrode and second electrode is set up an office according to actual conditions and selects,
Preferably in 0.2～20cm.
Example 16
In example 1-11, and on the basis of example 15, provided additionally it is possible to be preferably added reference electrode when electroplating
Reference potential, reference electrode preferably adopts calomel electrode or silver-silver chloride electrode, keeps the temperature of electroplate liquid in electroplate liquid
At 20～80 DEG C, this preferred embodiment to realize the temperature keeping with water bath with thermostatic control.
Example 17
As shown in figure 1, in example 1-11, the substrate of copper-depositing on surface zinc-tin metallic film is first carried out heating
To Jackson's alloy thin-film material, that is, carry out alloying annealing, specific as follows, take out the lining of depositing copper-zinc-tin metallic film
Bottom ultra-pure water washes away the foreign ion of the attachment on surface, and is dried, and is preferably dried up using nitrogen；By copper zinc-tin metallic film
Carry out thoroughly cleaning, reduce the impact to film quality and further battery efficiency for the foreign ion in plating solution, improve thin-film material
Quality.Can be made annealing treatment in tube furnace or other equipment, metallic film annealing temperature is 250 DEG C, programming rate
For 10 DEG C/s, temperature retention time is 30min, and annealing furnace internal gas pressure is 0.01atm, and gas flow is 40sccm, natural cooling.
Example 18
In example 1-11, the substrate of copper-depositing on surface zinc-tin metallic film is first carried out heating and obtains the conjunction of copper zinc-tin
Gold thin film material, that is, carry out alloying annealing, specific as follows, take out the substrate ultra-pure water of depositing copper-zinc-tin metallic film
Wash away the foreign ion of the attachment on surface, and be dried, preferably dried up using nitrogen；Can enter in tube furnace or other equipment
Row annealing, metallic film annealing temperature is 330 DEG C, and programming rate is 10 DEG C/s, and temperature retention time is 20min, in annealing furnace
Air pressure is 0.01atm, and gas flow is 50sccm, natural cooling.
Example 19
In example 1-11, the substrate of copper-depositing on surface zinc-tin metallic film is first carried out heating and obtains the conjunction of copper zinc-tin
Gold thin film material, that is, carry out alloying annealing, specific as follows, the substrate taking out depositing copper-zinc-tin metallic film is in tube furnace
Or made annealing treatment in other equipment, metallic film annealing temperature is 380 DEG C, and programming rate is 10 DEG C/s, and temperature retention time is
40min, annealing furnace internal gas pressure is 0.03atm, and gas flow is 60sccm, natural cooling.
Example 20
In example 1-11, the substrate of copper-depositing on surface zinc-tin metallic film is first carried out heating and obtains the conjunction of copper zinc-tin
Gold thin film material, that is, carry out alloying annealing, specific as follows, take out the substrate ultra-pure water of depositing copper-zinc-tin metallic film
Wash away the foreign ion of the attachment on surface, and be dried, preferably dried up using nitrogen；Can enter in tube furnace or other equipment
Row annealing, metallic film annealing temperature is 300 DEG C, and programming rate is 10 DEG C/s, and temperature retention time is 20min, in annealing furnace
Air pressure is 0.03atm, and gas flow is 50sccm, natural cooling.
Example 21
In example 1-11, the substrate of copper-depositing on surface zinc-tin metallic film is first carried out heating and obtains the conjunction of copper zinc-tin
Gold thin film material, that is, carry out alloying annealing, specific as follows, take out the substrate ultra-pure water of depositing copper-zinc-tin metallic film
Wash away the foreign ion of the attachment on surface, and be dried, preferably dried up using nitrogen；Can enter in tube furnace or other equipment
Row annealing, metallic film annealing temperature is 400 DEG C, and programming rate is 10 DEG C/s, and temperature retention time is 50min, in annealing furnace
Air pressure is 0.02atm, and gas flow is 40sccm, natural cooling.
Example 22
In example 1-11, the substrate of copper-depositing on surface zinc-tin metallic film is first carried out heating and obtains the conjunction of copper zinc-tin
Gold thin film material, that is, carry out alloying annealing, specific as follows, take out the substrate ultra-pure water of depositing copper-zinc-tin metallic film
Wash away the foreign ion of the attachment on surface, and be dried, preferably dried up using nitrogen；Can enter in tube furnace or other equipment
Row annealing, metallic film annealing temperature is 200 DEG C, and programming rate is 10 DEG C/s, and temperature retention time is 60min, in annealing furnace
Air pressure is 0.02atm, and gas flow is 50sccm, natural cooling.
Example 23
In example 1-22, copper zinc-tin thin-film material or Jackson's alloy thin-film material are exposed to sulfur-bearing atmosphere, high temperature
During process, heat in the tube furnace of argon gas atmosphere；During process, temperature is 585 DEG C, and programming rate is 5 DEG C/min, insulation
Time is 30 minutes, and annealing furnace internal gas pressure is 0.1atm, and gas flow is 50sccm, and the sulfiding gas of employing are sulfur vapor, will
Sulphur powder is put in graphite, further with putting into participation heating in tube furnace, forms sulfur vapor.
Example 24
In example 1-22, copper zinc-tin thin-film material or Jackson's alloy thin-film material are exposed to sulfur-bearing atmosphere high temperature
During process, heat in the tube furnace of nitrogen atmosphere；During process, sulfuration annealing temperature is 600 DEG C, and programming rate is 10
DEG C/min, temperature retention time is 10 minutes, and annealing furnace internal gas pressure is 0.1atm, and gas flow is 100sccm, the sulfiding gas of employing
For hydrogen sulfide.
Example 25
In example 1-22, copper zinc-tin thin-film material or Jackson's alloy thin-film material are exposed to sulfur-bearing atmosphere high temperature
During process, heat in tube furnace；During process, sulfuration annealing temperature is 620 DEG C, and programming rate is 10 DEG C/min, insulation
Time is 20 minutes, and annealing furnace internal gas pressure is 0.2atm, and gas flow is 80sccm, and the sulfiding gas of employing are artificial gold.
Example 26
In example 1-22, copper zinc-tin thin-film material or Jackson's alloy thin-film material are exposed to sulfur-bearing atmosphere high temperature
During process, heat in the tube furnace of argon gas atmosphere；During process, sulfuration annealing temperature is 620 DEG C, and programming rate is 10
DEG C/min, temperature retention time is 25 minutes, and annealing furnace internal gas pressure is 0.2atm, and gas flow is 90sccm, the sulfiding gas of employing
For hydrogen sulfide.
Example 27
In example 1-22, copper zinc-tin thin-film material or Jackson's alloy thin-film material are exposed to sulfur-bearing atmosphere high temperature
During process, put it in the graphite added with sulphur powder, heat in tube furnace；During process, temperature is 700 DEG C, heats up
Speed is 5 DEG C/min, and temperature retention time is 1 minute, and annealing furnace internal gas pressure is 0.15atm, and gas flow is 60sccm.
Example 28
In example 1-22, copper zinc-tin thin-film material or Jackson's alloy thin-film material are exposed to sulfur-bearing atmosphere high temperature
During process, heat in the tube furnace of nitrogen atmosphere；During process, sulfuration annealing temperature is 400 DEG C, and programming rate is 15
DEG C/min, temperature retention time is 40 minutes, and annealing furnace internal gas pressure is 0.15atm, and gas flow is 70sccm, the sulfiding gas of employing
For artificial gold.
Example 29
In example 1-11, and in example 17-22, by copper zinc-tin thin-film material or or Jackson's alloy thin-film material put
It is heated to high temperature to be processed such that it is able to be prepared the more superior copper zinc tin sulfur selenium of performance thin in sulfur-bearing and selenium atmosphere
Membrane material, condition during process is as shown in embodiment 23-28；Wherein, sulphur powder can be replaced by the sulphur powder mixing and selenium powder, jointly
Put in graphite, place in tube furnace and heated；Form the mixed vapour of sulphur and selenium；When sulphur passes through hydrogen sulfide and sulfuration
When tin adds, selenium also can be added by the form of selenium steam；Wherein by the control of sulphur and selenium different content such that it is able to
The content of sulphur and selenium in copper zinc tin sulfur selenium thin-film material is adjusted, thus meeting different use demands.
Example 30
In example 1-29, film-substrate to be plated adopts conductive substrates, and this example is with substrate as metal forming with polyphosphazene polymer
As a example the flexible substrate of compound film, preferably using flexible stainless steel, substrate is surpassed respectively through acetone, ethanol, deionized water
30 minutes post-dryings of sound are standby；On substrate can also one layer of molybdenum of electrochemical deposition, thickness be about 1 micron.
Example 31
In example 30, film-substrate to be plated adopts conductive substrates, and this example is with substrate as metal forming with high molecular polymerization
As a example the flexible substrate of thing film, preferably using flexible stainless steel, can be filled by the preparation of reel-to-reel mode as shown in Figure 7
Put, the copper zinc-tin thin-film material of the preparation present invention.
Example 32
In example 1-29, film-substrate to be plated adopts conductive substrates, and this example is with substrate as metal substrate, silicon chip and plating
As a example having the glass substrate of conductive film or the rigid substrate of ceramic substrate, preferred simple glass, by glass substrate through third
Ultrasonic 30 minutes post-dryings are standby respectively for ketone, ethanol, deionized water, need one layer of molybdenum of electron beam evaporation plating on a glass substrate, thick
Degree is about 1 micron；Molybdenum can also be replaced with metal including gold, copper and aluminium, the thickness of metal is 0.1～10 micron.Logical
Cross using molybdenum, gold, copper and aluminium film formed back contact so as to there be good Ohmic contact and absorbed layer between, decrease
Interfacial state between the two；Ensure that its excellent characteristics of output power using its excellent electric conductivity；Simultaneously with thereon
Copper zinc-tin absorbs layer material and chemical reaction does not occur it is ensured that the stability of thin-film material is additionally it is possible to good being attached to is to be plated
On film-substrate.
Example 33
In example 1-29, film-substrate to be plated adopts conductive substrates, and this example is with substrate as metal substrate, silicon chip and plating
As a example having the glass substrate of conductive film or the rigid substrate of ceramic substrate, preferred soda-lime glass, by substrate through acetone, second
Ultrasonic 30 minutes post-dryings are standby respectively for alcohol, deionized water, sputter one layer of copper by magnetron sputtering method, thickness is about on substrate
1 micron；Copper can also be replaced with metal oxide including ito, fto and azo, the thickness of metal oxide is 0.1～10
Micron.
Example 34
In example 1-29, film-substrate to be plated adopts conductive substrates, and this example is with substrate as metal substrate, silicon chip and plating
As a example having the glass substrate of conductive film or the rigid substrate of ceramic substrate, preferably molybdenum plate, by substrate through acetone, second
Ultrasonic 30 minutes post-dryings are standby respectively for alcohol, deionized water.Sem figure as shown in Figure 2, as can be seen from the figure after sulfuration annealing
The smooth densification of film surface, particle is uniformly distributed, and almost without cavity between particle, suitable further battery preparation.As Fig. 3
Shown xrd figure, for czts (copper-zinc-tin-sulfur) film using electrochemical deposition, is heated at high temperature in sulfur-bearing atmosphere
The effect of reason is particularly significant, that is, the sulfuration annealing to czts film.Can be seen that all films from xrd diffraction maximum
All assume czts stronger (112), (211), (200), (220) and (312) characteristic peak, in addition it was found that mo substrate
(110) and (211) diffraction maximum.Due to cu2znsns4, zns and cu2sns3Diffraction maximum very nearly the same, therefore adopt further
Raman is tested.As shown in figure 4, raman in figure is in 251cm-1、287cm-1、338cm-1And 368cm-1The vibration peak at place is all
Corresponding be czts thing phase, this analysis result with xrd coincide.It is not detected by zns and cu2sns3Thing phase, this is described
The czts thing phase purity of bright method preparation is high.The analysis result of other examples is identical, is or else repeated.
Example 35
On the basis of example 1-34, prepare the controlled copper zinc-tin thin-film material of composition, wherein copper zinc-tin film material
The thickness of material is 500～5000 nanometers；In this preferred embodiment, with the thickness of copper zinc-tin thin-film material for 1000～3000 nanometers,
Copper zinc-tin thickness of metal film is 700～1500 nanometers.
Example 36
On the basis of example 1-34, then copper zinc-tin thin-film solar cells can be obtained as follows, concrete step
Suddenly it is that cadmium sulfide cushion is deposited on copper zinc-tin film；Transparent conductive oxide i- is deposited respectively on cadmium sulfide cushion
Copper-zinc-tin-sulfur film solar cell is obtained after zno film and ito film or azo film.
Example 37
In example 36, the thickness of cadmium sulfide cushion is 40～150 nanometers, is deposited using chemical bath method.
Example 38
In example 36, the deposit thickness of transparent conductive oxide i-zno film is 50～150 nanometers；Delay in cadmium sulfide
Rush the azo film that deposit thickness on layer is 300～900 nanometers；I-zno film and azo film are sunk using magnetron sputtering method
Long-pending.Wherein, based on the molybdenum glass described in by example 34, then deposition i-zno film and azo film obtain copper-zinc-tin-sulfur is thin
The sem figure of film solar cell, as shown in Figure 5；Its i-v figure is as shown in fig. 6, inhaled with the czts film after the annealing of this experiment condition
Receive the battery device of the mo glass/czts/cds/i-zno/azo structure of layer preparation, in room temperature am1.5 and 1000w/m2Condition
Under the i-v characteristic curve of device that records, test result is as follows: open-circuit voltage (voc) is 466mv, short-circuit current density (jsc)
For 8.05ma/cm2, fill factor, curve factor (ff) is 42.04%.Battery efficiency is 1.60%, obtains the method for the invention system first
Standby battery efficiency.
Example 39
In example 36, the deposit thickness of transparent conductive oxide i-zno film is 50～150 nanometers；Delay in cadmium sulfide
Rush the ito film that deposit thickness on layer is 50～250 nanometers；I-zno film and ito film are sunk using magnetron sputtering method
Long-pending.
The above, only presently preferred embodiments of the present invention, not the present invention is done with any pro forma restriction.Any ripe
Know those skilled in the art, without departing under technical solution of the present invention ambit, described above technology contents all can be utilized
Technical solution of the present invention is made with many possible variations and modification, or the Equivalent embodiments being revised as equivalent variations.Therefore, all
It is the content without departing from technical solution of the present invention, the technology of a present invention any changed or repaiied to made for any of the above embodiments
Decorations, belong to the protection domain of the technical program.
Claims (13)
1. a kind of preparation method of copper zinc-tin thin-film material is it is characterised in that comprise the steps:
1) copper zinc-tin thin-film material contains at least copper, zinc and three kinds of base metal elements of tin；Three kinds of main body gold are contained in electroplate liquid
Belong to any two kinds in element；Annex solution contains the third base metal element lacking in described electroplate liquid；
2) there is at least one conductive electrode in electroplate liquid as first electrode, film-substrate to be plated is as second electrode；Described
Film-substrate to be plated be the substrate that conductive substrates or surface are coated with conductive film；
3), when being energized between first electrode and second electrode, speed control adds annex solution, that is, start to deposit simultaneously cupric, zinc and
The film of three kinds of metals of tin, obtains the substrate of copper-depositing on surface zinc-tin metallic film, as copper zinc-tin thin-film material；Electroplating
Cheng Zhong, second electrode current potential opposite first pole is negative.
2. a kind of preparation method of the copper zinc-tin thin-film material according to claim 1 is it is characterised in that in step 3) it
Afterwards, the silicon of copper-depositing on surface zinc-tin metallic film is processed at a temperature of 200～400 DEG C and obtain copper zinc in 20～60 minutes
Tin alloy film material.
3. a kind of preparation method of the copper zinc-tin thin-film material according to claim 1 or 2 is it is characterised in that in step
3) after, copper zinc-tin thin-film material or Jackson's alloy thin-film material are exposed to sulfur-bearing atmosphere, are heated to 400～700 DEG C of temperature
The lower process of degree 1～40 minute, prepares copper-zinc-tin-sulfur film material.
4. a kind of preparation method of the copper zinc-tin thin-film material according to claim 1 or 2 is it is characterised in that in step
3), after, copper zinc-tin thin-film material or Jackson's alloy thin-film material are exposed to sulfur-bearing and selenium atmosphere, are heated to 400～700
Process 1～40 minute at a temperature of DEG C, prepare copper zinc tin sulfur selenium thin-film material；In thin-film material, the ratio of sulphur and selenium, passes through
The ratio controlling sulphur and selenium in atmosphere is adjusted.
5. a kind of preparation method of the copper zinc-tin thin-film material according to claim 1 is it is characterised in that step 1) in electricity
Plating solution is dissolved in water and is made by the slaine of zinc-tin or copper and tin or zinc-tin and complex compound, respective salt concentration range be 0.01～
1m, complex compound is hydroxide, thiosulfate, sulphite, citrate, pyrophosphate, tartaric acid, tartrate and cyanogen
One or more of compound, complex concentration scope is 0.01～0.5m.
6. a kind of preparation method of the copper zinc-tin thin-film material according to claim 1 or 5 is it is characterised in that step 1)
Middle annex solution is dissolved in water by the third plating metal salt and complex compound and makes, and salt concentration range is 0.01～1m, and complex compound is
In hydroxide, thiosulfate, sulphite, citrate, pyrophosphate, tartaric acid, tartrate and cyanide one
Plant or several, complex concentration scope is 0.1～0.5m.
7. a kind of preparation method of the copper zinc-tin thin-film material according to claim 1 is it is characterised in that step 2) in,
The plated film part of the addition total amount submergence film-substrate to be plated of electroplate liquid and annex solution；Film-substrate to be plated is connected with negative electrode, the
One electrode is connected with anode, has been independently arranged reference electrode in electroplate liquid；Electroplate liquid ph value is adjusted to 2～6 before plating；During plating
Applied voltage -10～0v between the first electrode and the second electrode, distance is 0.2～20cm, and during plating, electroplate liquid keeps 20-80
DEG C constant temperature.
8. a kind of copper zinc-tin thin-film material according to claim 1 preparation method it is characterised in that adopt surface
It is coated with the substrate of conductive film, conductive film is metal or metal-oxide film that thickness is 0.1～10 micron.
9. a kind of preparation method of the copper zinc-tin thin-film material according to claim 1 or 8 is it is characterised in that described treat
Plating film-substrate is rigid substrate, and rigid substrate selects from metal substrate, silicon chip and the glass substrate being coated with conductive film or pottery
Ceramic liner bottom.
10. a kind of preparation method of the copper zinc-tin thin-film material according to claim 9 is it is characterised in that described gold
Belong to substrate to select from copper sheet, aluminium flake and stainless steel substrates；Described glass substrate selects certainly to be coated with the glass of fto or be coated with ito's
Glass.
A kind of preparation method of the 11. copper zinc-tin thin-film materials according to claim 1 or 8 is it is characterised in that described treat
Plating film-substrate is the flexible substrate selecting from metal forming or polymer membrane.
A kind of preparation method of the 12. copper zinc-tin thin-film materials according to claim 11 is it is characterised in that described is soft
Property substrate with reel-to-reel mode pass through electroplate liquid, prepare copper zinc-tin metallic film on flexible substrates.
A kind of 13. preparation methods of copper-zinc-tin-sulfur based solar battery are it is characterised in that any one in claim 1～12
A kind of step 3 of the preparation method of copper zinc-tin thin-film material described in) after, also comprise the steps: in copper zinc-tin film
Copper-zinc-tin-sulfur base solar is obtained after cadmium sulfide cushion and zno film and ito film or azo film are sequentially depositing on material
Battery.
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| CN104409566A (en) * | 2014-11-06 | 2015-03-11 | 云南师范大学 | Two-electrode electrochemical preparation method of copper zinc tin sulfide thin film material |
| CN104862753B (en) * | 2015-04-18 | 2020-02-07 | 云南师范大学 | Electrochemical preparation method of copper-zinc-tin-sulfur film absorption layer |
| CN104962871B (en) * | 2015-05-25 | 2018-04-27 | 同济大学 | A kind of high conductivity aluminum alloy films and preparation method thereof |
| CN108428765A (en) * | 2018-03-23 | 2018-08-21 | 北京梦之墨科技有限公司 | A kind of metallic film preparation process |
| CN109585581A (en) * | 2018-12-03 | 2019-04-05 | 江苏中宇光伏科技有限公司 | A kind of preparation method of solar battery sheet electrode |
| CN110611002B (en) * | 2019-09-24 | 2021-09-24 | 南开大学 | Preparation method of solar cell with P-doped Mo electrode |
| CN110611001B (en) * | 2019-09-24 | 2021-09-28 | 南开大学 | Method for preparing solar cell by using phosphate |
| CN113078225A (en) * | 2021-03-29 | 2021-07-06 | 南京邮电大学 | Copper-zinc-tin-sulfur-selenium semitransparent solar cell device and preparation method thereof |
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